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Ref1: Terthiophene Photophysics Revisited: Independence of the Triplet Quantum Yield on the Excitation Wavelength Ref2: Ground-State Structure and Excited-State Dynamics of a Donor–Acceptor Complex with Two Charge-Transfer Bands Ref3: Boramidine: a boron-based photoacidic fluorophore Ref4: Controlling the spatial distribution of electronic excitation in asymmetric D-A-D' and symmetric D'-A-D-A-D' electron donor-acceptor molecules Ref5: Tethered Enantiopure Boramidines for Advanced Chiroptical Studies Ref6: Structural and solvent modulation of symmetry-breaking charge-transfer pathways in molecular triads Ref7: Excited-State Symmetry Breaking and Localization in a Noncentrosymmetric Electron Donor-Acceptor-Donor Molecule Ref8: Excitation-Wavelength-Dependent Photophysics of a Torsionally Disordered Push-Pull Dye Ref9: Core-Alkynylated Fluorescent Flippers: Altered Ultrafast Photophysics to Track Thick Membranes Ref10: Axially-Chiral Boramidine for Detailed (Chir)optical Studies Ref11: Antenna Effect in Noble Metal-Free Dye-Sensitized Photocatalytic Systems Enhances CO2-to-CO Conversion Ref12: Controlling Symmetry-Breaking Charge Separation in Pyrene Bichromophores Ref13: Dye-Sensitized Photocatalysis: Hydrogen Evolution and Alcohol-to-Aldehyde Oxidation without Sacrifical Electron Donor Ref14: Excited-State Symmetry Breaking in Solvent Mixtures Ref15: Photoinduced Electron Transfer between Dipolar Reactants: Solvent and Excitation Wavelength Effects    Parcourir les références
Terthiophene Photophysics Revisited: Independence of the Triplet Quantum Yield on the Excitation Wavelength
J. Wega, F. Guignard and E. Vauthey
ref1697

A significant part of our understanding of the excited-state properties of polythiophenes comes from studies of smaller oligothiophenes, which have a better-defined structure. Among them, terthiophene (3T) was reported to have an excitation-wavelength dependent triplet quantum yield, ΦT. This was explained by the opening of a second intersystem crossing (ISC) pathway upon the high-energy excitation of distorted molecules. Here, we reinvestigate the excited-state dynamics of 3T in solvents of various viscosity and in a polymer film. Our results reveal that, although different subpopulations are excited upon high- and low-energy irradiation, the ISC dynamics, and hence ΦT, are the same. We show that the distorted molecules excited at short wavelength undergo rapid planarization independent of the viscosity of the environment before significant ISC takes place. The apparent increase of ΦT with increasing excitation wavelength reported earlier can be explained by the neglect of the early relaxation dynamics.

Journal of Physical Chemistry Letters, 16 , 2025 , p7984 -7989

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